Xanthogen disulphides with functional groups

ABSTRACT

This invention relates to xanthogen disulphides of the formula ##STR1## in which R is the same or different and denotes the following groups: ##STR2## WHEREIN X = H, alkyl, aryl, aralkyl or halogen 
     n = 1 to 20, 
     A process for preparing them, a process for polymerizing dienes and α-olefines in the presence of these particular xanthogen disulphides and to vulcanizable rubber mixtures consisting of an uncross-linked benzene soluble chloroprene homopolymer or copolymer which is prepared in the presence of said xanthogen disulphides.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 570,098 filedApr. 21, 1975 which, in turn, is a division of application Ser. No.440,014 filed Feb. 6, 1974 and now U.S. Pat. No. 3,926,912.

This invention relates to certain xanthogen disulphides with functionalgroups, a process for preparing them, a process for polymerising dienesand α-olefines in the presence of these particular xanthogen disulphidesand to vulcanisable rubber mixtures consisting of an uncross-linkedbenzene soluble chloroprene homopolymer or copolymer which is preparedin the presence of said xanthogen disulphides.

Xanthogen disulphides of this invention have the general formula I##STR3## in which R is the same or different and denotes the followinggroups: ##STR4## WHEREIN X= H, alkyl, aryl, aralkyl or halogen

n= 1 to 20;

Alkyl groups containing 1 to 6 carbon atoms (methyl, ethyl, isopropyl,hexyl), phenyl, naphthyl, benzyl, chlorine, bromine and iodine beingpreferred.

The invention particularly relates to those xanthogen disulphides of thegeneral formula I in which the two groups R are identical and the groupsX denotes hydrogen or alkyl (preferably C₁ - C₆).

Another object of this invention is a process for producing xanthogendisulphides of formula I wherein an alcohol of the formula ROH in whichR has the meaning indicated above is reacted with carbon disulphide inthe presence of a strong alkali to form the alkali metal xanthate whichis then oxidized to the xanthogen disulphide. Alcohols with thefollowing groups R are particularly suitable for this process: ##STR5##

The process is generally carried out as follows: Starting from anaqueous solution of an alkali, e.g. a 20- 50 % aqueous potassium orsodium hydroxide solution, approximately equimolar quantities of analcohol ROH (in which R has the meaning defined above) are added. Carbondisulphide is slowly added to this mixture. The carbon disulphide may beadded in equimolar quantities or in an excess. An exothermic reactionimmediately sets in to form the xanthate. During this reaction, themixture is cooled so that the reaction temperature does not rise above50° C.

The reaction may be represented as follows: ##STR6## in which M= alkalimetal and R has the meaning defined above.

The aqueous xanthate solution obtained is then oxidised to xanthogendisulphide by the addition of a suitable oxidising agent such ashydrogen peroxide or potassium peroxydisulphate (as aqueous solution).The water-insoluble xanthogen disulphide precipitates. It is separatedfrom the aqueous phase, e.g. by filtration or decanting, and dried. Thereaction may be represented as follows: ##STR7## R has the meaningdefined above.

This process is carried out similar to the process for producing dialkylxanthogen disulphides as described, for example, in Kirk-Othmer,"Encyclopedia of Chemical Technology", 2nd Edition, Vol. 22 (1970),pages 419- 429 and in Ullmann "Encyclopedie der Techn. Chemie" Vol. 18(1967) pages 718- 728.

Another object of this invention is a process for polymerising one ormore conjugated diolefines and copolymerising one or more conjugateddiolefines with α-olefines in the presence of radical forminginitiators, in the presence of xanthogen disulphides of the generalformula I as molecular weight modifiers. Particularly suitableconjugated diolefines are those which contain 4 to 8 carbon atoms suchas butadiene, isoprene, piperylene, chloroprene and2,3-dichlorobutadiene.

In more detail this invention relates to a process for producingchloroprene polymers which are easy to process, wherein

(a) 60 to 100 parts by weight of chloroprene and 40 to 0 parts by weightof a diene in which the hydrogen atoms may be partly or completelysubstituted by halogen atoms and/or of an α-olefine are polymerised inthe presence of 0.05 to 30 parts by weight, preferably 0.15 to 5 partsby weight and especially 0.15 to 1 parts by weight of a xanthogendisulphide of the formula I in aqueous dispersion.

The α-olefines used are preferably acrylonitrile, styrene andethylacrylate. These comonomers are usually present in quantities of upto 40% by weight, based on the diolefine. Suitable radical formingpolymerisation catalysts are, for example, peroxides and azo compoundsor so-called redox systems. The following are examples: Cumenehydroperoxide, pinene hydroperoxide, potassium peroxidisulphate,tert.-butyl peroxide, azo-bis-isobutyronitrile. Redox systems are:peroxides, e.g. cumene hydroperoxide, in combination with reducingcompounds, e.g. formaldehyde sulphoxylate, iron salts or formamidinesulphinic acid.

The polymerisation is preferably carried out in aqueous emulsion. Anaqueous emulsifier solution starting from an "aqueous phase" whichcontains at least 0.1 to 5% by weight of an emulsifier is provided.Suitable emulsifiers are e.g. alkali metal alkyl sulphonates, alkalimetal sulphates, long chain carboxylic acids, resinic acids andpolyether alcohols. The monomer or monomers together with 0.05 to 30% byweight, preferably 0.15 to 1% by weight, based on the monomers, of adialkylxanthogen disulphide of formula I are then emulsified in this"aqueous phase" and the radical forming initiator is added.Polymerisation is preferably carried out at temperatures of from -50° to100° C., preferably 5° to 50° C. This process is basically known forpolymerising chloroprene, e.g. from U.S. Pat. Nos. 3,042,652; 3,147,317and 3,147,318.

When 50 to 100%, preferably 50 to 70% of the monomers have beenpolymerised, unreacted monomer is removed and then the polymer isrecovered from the aqueous emulsion by electrolyte precipitation offreezing coagulation and drying. In this polymerisation the xanthogendisulphide of formula I act as molecular weight modifiers, i.e. theyreduce the molecular weight of the resulting polymers compared with themolecular weight of polymers obtained in the absence of xanthogendisulphide. This becomes apparent by comparing the Mooney viscosities ofthe resulting products.

The xanthogen disulphides of formula I are particularly suitable formodifying the molecular weight of chloroprene polymers. Chloroprenepolymers obtained in their presence yield vulcanisates of improvedmechanical properties.

This is particularly pronounced in mixtures of uncross-linked benzenesoluble polychloroprenes made in accordance with this invention andbenzene insoluble, slightly cross-linked polychloroprenes. Thesemixtures are easy to process and their vulcanisates have particularlyhigh tensile strength.

The tensile strength of these vulcanisated polymers can be even furtherimproved by vulcanising in the presence of agents, such as maskeddiisocyanates, which react with the end groups of the xanthogendisulphides.

Another object of this invention is therefore a mixture of anuncross-linked, benzene soluble chloroprene polymer (a) made fromchloroprene and optionally up to 40% by weight (based on the monomermixture) of an α-olefine in the presence of 0.05- 30 % by weight (basedon the monomers) of a xanthogen disulphide of formula I and across-linked, benzene insoluble chloroprene polymer (b).

The benzene soluble chloroprene polymer (a) in this mixture is theproduct described above.

In more detail this invention relates to a process for producingchloroprene polymer mixtures which are easy to process wherein

(a) 60 to 100 parts by weight of chloroprene and 40 to 0 parts by weightof a diene in which the hydrogen atoms may be partly or completelysubstituted by halogen atoms and/or of an α-olefine are polymerised inthe presence of 0.05 to 30 parts by weight, preferably 0.15 to 5 partsby weight and especially 0.15 to 1 part by weight of a xanthogendisulphide of the formula I in aqueous dispersion to produce anuncross-linked, benzene soluble polymer which is then mixed with

(b) a cross-linked, benzene insoluble chloroprene homopolymer orcopolymer consisting of 80 to 100 parts by weight of chloroprene and 20to 0 parts by weight of a divinyl compound and/or an α-olefine, thecomponents A and B being mixed in a ratio by weight of between 20:1 and1:20, preferably between 1:1 and 7:1.

The invention relates also to mixtures of 5 to 95 parts by weight,preferably 55 to 90 parts by weight of an uncross-linked, benzenesoluble chloroprene homopolymer or copolymer consisting of 60 to 100parts by weight of chloroprene and 40 to 0 parts by weight of a diene inwhich the hydrogen atoms may be partly or completely replaced by halogenatoms and/or of an α-olefine which has been prepared in the presence of0.05 to 30 parts by weight, preferably 0.15 to 5 parts by weight andespecially 0.15 to 1 part by weight of a xanthogen disulphide of formulaI and 95 to 5 parts by weight, preferably 45 to 10 parts by weight, of across-linked, benzene insoluble chloroprene homopolymer or copolymer of80 to 100 parts by weight of chloroprene and 20 to 0 parts by weight ofa divinyl compound and/or an α-olefine.

Suitable benzene insoluble cross-linked chloroprene polymers can beprepared by various methods which yield cross-linked polymer in thelatex form, for example the chloroprene may be polymerised to a highdegree of conversion in the absence of a chain transfer agent or withonly small quantities of such agent, e.g. an alkylmercaptan ordialkylxanthogen disulphide. A suitable method of carrying out such aprocess to a high degree of polymerisation has been described, forexample in U.S. Pat. No. 3,147,317. In another method of makingcross-linked chloroprene polymer a comonomer which is capable ofcopolymerising with the chloroprene and which contains two or morepolymerisable double bonds is added in the polymerisation. Comonomerssuitable for this purpose are, for example, divinylbenzene and esters ofmethacrylic acid and polyhydroxy compounds such as alkylene glycols,dihydroxybenzene or trimethylpropane.

Cross-linked chloroprene polymers are obtained by the same methods asknown for making benzene soluble chloroprene polymers but monomerconversion is raised to, e.g. 90 to 100%.

In another method of preparing suitable cross-linked chloroprenepolymers the latex of an uncross-linked chloroprene polymer is subjectedto a post-treatment which effects cross-linking. Such post-treatment ise.g. irradiation according to U.S. Pat. No. 3,042,652 and treatment withan organic peroxy compound according to U.S. Pat. No. 3,147,318.

In the cross-linked polymer part of the chloroprene, up to about 20 %can be replaced by another monomer. Suitable comonomers are the same aswith the benzene soluble polymers described above.

The benzene insoluble chloroprene polymer is preferably a copolymer ofchloroprene and 2 to 20 % by weight (based on chloroprene) of a diesterof a dihydric aliphatic alcohol and an acrylic acid. These diesters havethe general formula ##STR8## in which R₁ to R₂ represent hydrogen, alkylcontaining 1 to 4 carbon atoms or chlorine and X represents an alkylenegroup containing 2- 20 carbon atoms.

The following are examples of such compounds: ethylene dimethacrylate,propylene dimethacrylate, butylene dimethacrylate, isobutylenedimethacrylate, ethylene diacrylate, propylene diacrylate, butylenediacrylate and isobutylene diacrylate.

These products are made in accordance with the usual methods ofpolymerising chloroprene and of copolymerising butadiene andacrylonitrile in aqueous emulsion. The procedure and the productsobtained from it are disclosed in British Pat. No. 1,158,970.

The components of the elastomer mixture are preferably combined byvigorously mixing the latices and then recovering the solid polymermixture by the usual methods, e.g. freezing coagulation (U.S. Pat. No.2,187,146) or drying on rollers (U.S. Pat. No. 2,914,497). Elektrolyteprecipitation is also possible. Alternatively, the components can berecovered individually by the usual methods and then be mixedmechanically, e.g. by kneading on mixing rollers or in an internal mixersuch as a Banbury mixer or a Werner-Pfleiderer mixer.

In the case of polychloroprene, the weight ratio of benzene solublecomponent (a) to cross-linked component (b) may be from 20:1 to 1:20,preferably from 1:1 to 7:1. The mixture should contain at least 50 % byweight of benzene soluble component (a).

The polychloroprene mixtures according to the invention can becompounded to form vulcanisable rubber mixtures and vulcanised in thesame way as conventional polychloroprenes. They are used for allpurposes for which polychloroprenes are suitable.

Their primary advantage is improved processing compared to benzenesoluble polychloroprenes and to benzene insoluble polychloroprenes takenalong. Compared to known mixtures of benzene soluble and benzeneinsoluble polychloroprenes, their thermal stability is substantiallyimproved.

When benzene soluble polychloroprenes made in the presence of xanthogendisulphides of formula I are compared to those made in the presence ofmercaptans as molecular weight modifiers, they are found to be superiorin the tensile strengths of the vulcanisates. The tensile strengths canbe even further improved by vulcanising with masked diisocyanates.

EXAMPLES OF THE PREPARATION OF XANTHOGEN DISULPHIDES WHICH CONTAINALKOXY GROUPS (A) EXAMPLE 1 Xanthogen disulphide of hexane triolmonoacetal

To prepare the xanthogen disulphide of hexane triol monoacetal, 88 g ofsodium hydroxide and 90 g of distilled water are introduced into a 3liter flask and the sodium hydroxide is dissolved with stirring. 292 gof hydroxy-hexane-1,2-diol acetal (hexantriolmonoacetal) of thefollowing formula a ##STR9## are then added and the reaction mixture isstirred for 2 hours. It is then cooled to 10° C. and 184 g of carbondisulphide are added dropwise with stirring. The temperature should notrise above 20° C. during this operation. When all the carbon disulphidehas been added, the whole mixture is stirred for a further 2 hours.

A solution consisting of 300 g of ammonium persulphate and 2 liters ofdistilled water is then added dropwise to the reaction mixture in whichthe xanthate has been formed. The xanthogen disulphide which is formedby oxidation is then removed from the aqueous phase, washed withdistilled water and taken up in ether, and the ethereal phase is driedwith anhydrous sodium sulphate. The solvent is removed in a rotaryevaporator. The yield of xanthogen disulphide is 360 g. ##STR10##

EXAMPLE 2 Xanthogen disulphide of hexane triol monoketal

To prepare the xanthogen disulphide of hexane triol monoketal, 88 g ofsodium hydroxide and 90 g of distilled water are introduced into a 3liter flask and the sodium hydroxide is dissolved with stirring. 348 gof 6-hydroxy-hexane-1,2-diolmonoketal (hexane triol monoketal of formulab ##STR11## are then added and the mixture then stirred for a further 2hours. The reaction mixture is then cooled to 10° C. and 184 g of carbondisulphide are added dropwise with stirring, during which time thetemperature should not rise above 20° C. Stirring is continued foranother 2 hours after all the carbon disulphide has been added.

A solution consisting of 300 g of ammonium persulphate and 2 liter ofdistilled water is then added dropwise into the reaction mixturecontaining the xanthate which has been formed in the reaction. Thexanthogen disulphide obtained by oxidation is then separated from theaqueous phase, washed with distilled water and taken up in ether and theethereal phase is dried with anhydrous sodium sulphate. The solvent isevaporated in a rotary evaporator. The yield of xanthogen disulphide is358 g. ##STR12##

EXAMPLE 3 Xanthogen disulphide of glycerol monoacetals

To prepare xanthogen disulphides of glycerol monoacetals, 88 g of sodiumhydroxide and 90 g of distilled water are introduced into a 3 l flaskand the sodium hydroxide is dissolved with stirring. 264 g of a mixtureof glycerol monoacetals of formulae C₁ and C₂ which are obtained byreacting glycerol with formaldehyde are then added and stirring iscontinued for 2 hours. ##STR13##

The reaction mixture is then cooled to 10° C. 184 g of carbon disulphideare then added dropwise with stirring; the temperature should not riseabove 20° C. during this operation. Stirring is continued for 2 hoursafter all the carbon disulphide has been added.

A solution consisting of 300 g of ammonium persulphate and 2 liters ofdistilled water is then added dropwise to the reaction mixture of theresulting xanthates. The xanthogen disulphides formed by oxidation arethen separated from the aqueous phase, washed with distilled water andtaken up with ether and the ethereal phase is dried with anhydroussodium sulphate. The solvent is removed in a rotary evaporator. Theyield of xanthogen disulphides is 250 g. ##STR14##

EXAMPLE 4 Xanthogen disulphide of glycerol monoketal

To prepare the xanthogen disulphide of glycerol monoketal, 88 g ofsodium hydroxide and 90 g of distilled water are introduced into a 3liter flask and the sodium hydroxide is dissolved with stirring. 266 gof the glycerol monoketal of formula d are then added. ##STR15## andstirring is continued for 2 hours. The reaction mixture is then cooledto 10° C. 176 g of carbon disulphide are then added with stirring; thetemperature should not rise above 20° C. during this operation. Afterall the carbon disulphide has been added, the reaction mixture isstirred for another 2 hours. A solution consisting of 300 g of ammoniumpersulphate and 2 liters of distilled water is then added dropwise tothe reaction mixture containing the resulting xanthate. The xanthogendisulphide obtained by oxidation is then separated from the aqueousphase, washed with distilled water and taken up in either and theethereal phase is dried with anhydrous sodium sulphate. The solvent isremoved in a rotary evaporator. The yield of xanthogen disulphide is 270g. ##STR16##

EXAMPLE 5 Xanthogen disulphide of 1,1,1-tris-hydroxymethyl-propanemonoacetal

To prepare the xanthogen disulphide of 1,1,1-tris-hydroxy-methyl-propanemonoacetal, 88 g of sodium hydroxide and 90 g of distilled water areintroduced into a 3 liter flask and the sodium hydroxide is dissolvedwith stirring. 292 g of the monoacetal of formula e ##STR17## are thenadded and stirring is continued for 2 hours. The reaction mixture isthen cooled to 10° C. and 176 g of carbon disulphide are added withstirring. The temperature should not rise above 20° C. during theaddition of carbon disulphide. The reaction mixture is stirred foranother 2 hours after all the carbon disulphide has been added. Asolution consisting of 300 g of ammonium persulphate and 2 liters ofdistilled water is then added dropwise to the reaction mixturecontaining the resulting xanthate. The xanthogen disulphide obtained onoxidation is then separated from the aqueous phase, washed withdistilled water and taken up in ether and the ethereal phase is driedwith anhydrous sodium sulphate. The solvent is removed in a rotaryevaporator. The yield of xanthogen disulphide is approximately 350 g.##STR18##

(B) I. Example of Polymerisation

The following phases are prepared separately and introduced into thepolymerisation vessel:

Monomer phase

100 parts by weight of chloroprene

y parts by weight of xanthogen disulphide of hexane triol monoacetal

Aqueous phase

120 parts by weight of distilled water

5 parts by weight of sodium salt of a disproportionated abietic acid

0.5 parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.5 parts by weight of sodium hydroxide

0.5 parts by weight of tetrasodium pyrophosphate

The quantity y of modifier is varied as follows:

y₁ = 0.5 parts by weight

y₂ = 0.75 parts by weight

y₃ = 0.80 parts by weight

y₄ = 1.00 parts by weight

After mixing the two phases, the temperature is raised to 43° C. andpolymerisation is initiated by an activator solution consisting of 2.5parts by weight of formamidine sulphinic acid and 97.5 parts by weightof distilled water. The activator solution is added dropwise asrequired.

When 65 to 70% of the monomer has been converted to polymer, theremaining monomer is removed by steam distillation and the polymer isisolated from the latex by electrolyte precipitation and dried.

The Mooney viscosities were found to vary with the quantities ofmodifier as follows:

    ______________________________________                                                Regulator      Mooney-viscosity                                       y       % by weight    ML-4'/100° C                                    ______________________________________                                        y.sub.1 0.5            130                                                    y.sub.2 0.75           57                                                     y.sub.3 0.80           50                                                     y.sub.4 1.00           32                                                     ______________________________________                                    

II. Example of polymerisation

The following phases were prepared separately and introduced into thepolymerisation vessel:

Monomer phase

100 Parts by weight of chloroprene

z Parts by weight of xanthogen disulphide of1,1,1-tris-hydroxymethylpropane monoacetal

Aqueous phase

120 Parts by weight of distilled water

5 Parts by weight of sodium salt of a disproportionated abietic acid

0.5 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.5 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodium pyrophosphate

The quantity z of modifier was varied as follows:

z₁ = 0.1 Part by weight

z₂ = 0.5 Part by weight

z₃ = 1.0 Part by weight

When the two phases have been mixed, the temperature is raised to 43° C.and polymerisation is initiated by an activator solution consisting of2.5 parts by weight of formamidine sulphinic acid and 97.5 parts byweight of distilled water. The activator solution is added dropwise asrequired.

When 65 to 70% of the monomer has been converted to polymer, theremaining monomer is removed by steam distillation and the polymer isisolated from the latex by electrolyte precipitation and dried.

The following Mooney viscosities were then measured in dependence on themodifier quantity z:

    ______________________________________                                                Regulator      Mooney viscosity                                       z       % by weight    ML-4'/100° C                                    ______________________________________                                        z.sub.1 0.1            140                                                    z.sub.2 0.5            92                                                     z.sub.3 1.0            23                                                     ______________________________________                                    

III. Example of polymerisation (Comparison example)

The following phases were prepared separately and introduced into thepolymerisation vessel:

Monomer phase

100 Parts by weight of chloroprene

0.45 Parts by weight of diisopropyl xanthogen disulphide

Aqueous phase

120 Parts by weight of distilled water

5 Parts by weight of sodium salt of a disproportionated abietic acid

0.5 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.5 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodium pyrophosphate

When the two phases have been mixed, the temperature is raised to 43° C.and polymerisation is released by an activator solution consisting of2.5 parts by weight of formamidine sulphinic acid and 97.5 parts byweight of distilled water. The activator solution is added dropwise asrequired.

When 65 to 70% of the monomer has been converted to polymer, theremaining monomer is removed by steam distillation and the polymer isisolated from the latex by electrolyte precipitation and dried. Thepolymer has a Mooney viscosity of approximately 44.

IV. Example of polymerisation (Comparison example)

The following phases were prepared separately and introduced into thepolymerisation vessel:

Monomer phase

100 Parts by weight of chloroprene

0.28 Parts by weight of n-DDM (normal dodecylmercaptan)

Aqueous phase

120 Parts by weight of distilled water

5 Parts by weight of sodium salt of a disproportionated abietic acid

0.5 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.5 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodiumpyrophosphate

When the two phases have been mixed, the temperature is raised to 43° C.and polymerisation is initiated with an activator solution consisting of2.5 parts by weight of formamidine sulphinic acid and 97.5 parts byweight of distilled water. The activator solution is added dropwise asrequired. When 65 to 70% of the monomer has been converted to polymer,the remaining monomer is removed by steam distillation and the polymeris isolated from the latex by electrolyte precipitation and dried. Thepolymer has a Mooney viscosity of approximately 43.

V. Example of polymerisation (Comparison example)

The following phases were prepared separately and introduced into thepolymerisation vessel:

Monomer phase

100 Parts by weight of chloroprene

0.4 Parts by weight of diethyl xanthogen disulphide

Aqueous phase

120 Parts by weight of distilled water

5 Parts by weight of sodium salt of a disproportionated abietic acid

0.5 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.5 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodium pyrophosphate

When the two phases have been mixed, the temperature is raised to 43° C.and polymerisation is initiated with an activator solution consisting of2.5 parts by weight of formamidine sulphinic acid and 97.5 parts byweight of distilled water. The activator solution is added dropwise asrequired. When 65 to 70% of the monomer has been converted to polymer,the remaining monomer is removed by a steam distillation and the polymeris isolated from the latex by electrolyte precipitation and dried. Thepolymer has a Mooney viscosity of approximately 43.

VI. Example of polymerisation (Comparison example)

The following phases were prepared separately and introduced into thepolymerisation vessel:

Monomer phase

100 Parts by weight of chloroprene

0.55 Parts by weight of xanthogen disulphide of ethylene glycolmonomethylether

Aqueous phase

120 Parts by weight of distilled water

5 Parts by weight of sodium salt of a disproportionated abietic acid

0.5 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.5 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodium pyrophosphate

When the two phases have been mixed, the temperature is raised to 43° C.and polymerisation is initiated with an activator solution whichconsists of 2.5 parts by weight of formamidine sulphinic acid and 97.5parts by weight of distilled water. The activator solution is addeddropwise as required. When 65 to 70% of the monomer has been convertedto polymer, the remaining monomer is removed by steam distillation andthe polymer is isolated from the latex by electrolyte precipitation anddried. The polymer has a Mooney viscosity of approximately 43.

VII. Example of polymerisation (Comparison example)

The following phases were prepared separately and introduced into thepolymerisation vessel:

Monomer phase

100 Parts by weight of chloroprene

0.55 Parts by weight of xanthogen disulphide of ethylene glycolmonoethyl ether

0.35 Parts by weight of sulphur

Aqueous phase

120 Parts by weight of distilled water

5 Parts by weight of sodium salt of a disproportionated abietic acid

0.7 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.8 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodium pyrophosphate

When the two phases have been mixed, the temperature is raised to 43° C.and polymerisation is initiated with an activator solution which has thefollowing composition: 1.3 Parts of distilled water, 0.04 parts ofpotassium persulphate and 0.04 parts of anthraquinone sulphonic acidsodium salt. The activator solution is added as required. When between65 and 95% of the monomer (depending on the desired viscosity) has beenconverted to polymer, the remaining monomer is removed by steamdistillation and the polymer is isolated by electrolyte precipitationand dried.

VIII. Example of polymerisation (Comparison example)

The following phases were prepared separately and introduced into thepolymerisation vessel:

Monomer phase

100 Parts by weight of chloroprene

0.4 Parts by weight of xanthogen disulphide of ethanol

0.35 Parts by weight of sulphur

Aqueous phase

120 Parts by weight of distilled water

5 Parts by weight of sodium salt of a disproportionated abietic acid

0.7 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.8 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodium pyrophosphate

When the two phases have been mixed, the temperature is raised to 43° C.and polymerisation is initiated with an activator solution of thefollowing composition: 1.3 Parts of distilled water, 0.04 parts ofpotassium persulphate and 0.04 parts of anthraquinone sulphonic acidsodium salt. The activator solution is added as required. When between65 and 95% of the monomer (depending on the desired viscosity) has beenconverted to polymer, the remaining monomer is removed by steamdistillation and the polymer isolated by electrolyte precipitation anddried.

IX. Example of polymerisation

The following phases are prepared separately and introduced into thepolymerisation vessel:

Monomer phase

100 Parts by weight of chloroprene

0.85 Parts by weight of xanthogen disulphide of hexanetriol monoacetal

0.35 Parts by weight of sulphur

Aqueous phase

120 Parts by weight of distilled water

5 Parts by weight of sodium salt of a disproportionated abietic acid

0.7 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.8 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodium pyrophosphate

When the two phases have been mixed, the temperature is raised to 43° C.and polymerisation is initiated with an activator solution of thefollowing composition:

1.3 Parts of distilled water, 0.04 parts of potassium persulphate and0.04 parts of anthraquinone sulphonic acid sodium salt. The activatorsolution is added as required. When between 65 and 95% of the monomer(depending on the desired viscosity) has been converted to polymer, theremaining monomer is removed by steam distillation and the polymer isisolated by electrolyte precipitation and dried.

The polymers prepared under I- IX are then mixed with the followingcomponents on rollers in the usual manner:

Formulation (α)

100 Parts by weight of polychloroprene

29 Parts by weight of inactive carbon black

0.5 Parts by weight of stearic acid

2.0 Parts by weight of phenyl-β-naphthylamine

4.0 Parts by weight of magnesium oxide

5.0 Parts by weight of zinc oxide

0.5 Parts by weight of ethylene thiourea

Formulation (β)

100 Parts by weight of polychloroprene

29 Parts by weight of inactive carbon black

0.5 Parts by weight of stearic acid

2.0 Parts by weight of phenyl-β-naphthylamine

1.0 Parts by weight of magnesium oxide

5.0 Parts by weight of zinc oxide

3.0 Parts by weight of TA-11 (R)

Vulcanization is carried out at 151° C. for 30 minutes. The vulcanizatesobtained have the properties shown below (Table 1). It can be seen fromTable 1 that the highest strength values are obtained when regulators inthe form of the particular xanthogen disulphides of formula K are used(Example I) Formulation α. The difference is particularly marked whenusing a vulcanization accelerator which responds to the modifiedxanthogen disulphides of Formula I (Example I) Formulation β. ##STR19##

                                      Table 1                                     __________________________________________________________________________                      Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                    I    III  IV   V    VI                                     __________________________________________________________________________    Formulation (α)                                                         Tensile strength (kg/cm.sup.2)                                                                  159  143  145  144  142                                     Elongation at break (%)                                                                         630  640  615  680  650                                     Modulus (300% elongation) kg/cm.sup.2                                                           48/123                                                                             43/107                                                                             42/112                                                                             45/105                                                                             48/111                                    (500% elongation)                                                           Hardness RT       57   55   53   58   57                                      Elasticity        56   54   52   56   54                                      Formulation (β)                                                          Tensile strength (kg/cm.sup.2                                                                   177  --   115  --   --                                      Elongation at break (%)                                                                         870  --   925  --   --                                      Modulus (300% elongation) kg/cm.sup.2                                                           37/92                                                                              --   18/44                                                                              --   --                                        (500% elongation)                                                           Hardness RT       37   --   48   --   --                                      Elasticity        30   --   53   --   --                                      __________________________________________________________________________

X. Example of Polymerisation (A)

Preparation of the benzene insoluble polychloroprene as one of thecomponents for preparing a mixture which has good properties for workingup.

The following components are introduced into a 40 liter autoclave whichis equipped with stirrer, thermometer and feed tubes and connected to acooling system:

14.4 l of salt-free water, 815 g of the sodium salt of adisproportionated abietic acid mixture, 72 g of a condensation productof an alkyl naphthalene sulphonic acid and formaldehyde, 36 g of sodiumhydroxide, and 60 g of tetrasodium pyrophosphate. A solution containingthe following constituents is then added: 10.620 g of chloroprene, 1.380g of ethylene glycol dimethacrylate, 34 g of n-dodecylmercaptan. Thereaction mixture is then heated to 43° C. and polymerisation isinitiated by dropwise addition of a catalyst solution containing thefollowing components:

2.5 g of formamidine sulphinic acid, dissolved in 97.5 g of distilledwater. When approximately 80% of the monomer has been polymerised,polymerisation is stopped by the addition of a stabilizer solution ofthe following composition:

5 g of phenothiazine, and 5 g of p-tert.-butyl-pyrocatechol in 500 g oftoluene. The latex is then freed from unreacted monomer.

(B)

Preparation of benzene soluble polychloroprene as one of the componentsfor the preparation of a mixture which has good properties for workingup.

Preparation of the benzene soluble polychloroprene is carried out inaccordance with polymerisation examples I, IV, V and VI.

XI. Preparation of a mixture of benzene soluble and benzene insolublepolychloroprene

85 Parts by weight of benzene soluble polymer component are mixed with15 parts by weight of benzene insoluble polymer component (X) in thelatex and the polymer is then isolated from the latex (Table II).

                  Table II                                                        ______________________________________                                             Benzene soluble   Benzene insoluble                                           polychloroprene   polychloroprene                                        XI   85 Parts by weight                                                                              15 parts by weight                                     ______________________________________                                        A     Polymer Example I Polymer Example X                                     B     Polymer Example IV                                                                              Polymer Example X                                     C     Polymer Example V Polymer Example X                                     D     Polymer Example VI                                                                              Polymer Example X                                     ______________________________________                                    

Polymers XI A to XI D are then mixed in accordance with Formulation αand Formulation β and vulcanized at 151° C. for 30 minutes.

I. PREPARATION OF UNCROSS-LINKED, BENZENE SOLUBLE CHLOROPRENE POLYMERSEXAMPLE 6 Monomer phase

100.00 Parts by weight of chloroprene

0.85 Parts by weight of xanthogen disulphide of the following formula##STR20##

Aqueous phase

120.0 Parts by weight of salt-free water

5.0 Parts by weight of sodium salt of a disproportionated abietic acid

0.5 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.5 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodium pyrosphosphate

When the two phases have been mixed, the temperature is adjusted to 43°C. and polymerisation is initiated with an activator solution consistingof 2.5 parts by weight of formamidine sulphinic acid and 97.5 parts byweight of salt-free water. The activator solution is added dropwise asrequired.

When 65 to 70% of the monomers have been polymerised, polymerisation isstopped by the addition of a radical acceptor, e.g. tertiary butylpyrocatechaol, and the remaining monomers are removed by steamdistillation. The Mooney viscosity ML-4'/100° C. of a sample which hasbeen isolated by electrolyte precipitation and drying is 45.

EXAMPLE 7 Monomer phase

100.00 Parts by weight of chloroprene

0.84 Parts by weight of xanthogen disulphide of the following formula##STR21##

Aqueous phase

120.0 Parts by weight of salt-free water

5.0 Parts by weight of sodium salt of a dispropionated abietic acid

0.5 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.5 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodium pyrophosphate

When the two phases have been mixed, the temperature is adjusted to 43°C. and polymerisation is initiated with an activator solution consistingof 2.5 parts by weight of formamidine sulphinic acid and 97.5 parts byweight of salt-free water. The activator solution is added dropwise asrequired.

When 65 to 70% of the monomers have been converted to polymer,polymerisation is stopped by the addition of a radical acceptor, e.g.tertiary butyl pyrocatechol, and the remaining monomers are removed bysteam distillation. The Mooney viscosity ML-4'/100° C. of a sample whichhas been isolated by electrolyte precipitation and drying is 45.

EXAMPLE 8 (Comparison Example) Monomer phase

100.00 Parts by weight of chloroprene

0.28 Parts by weight of n-dodecylmercaptan

Aqueous phase

120.0 Parts by weight of salt-free water

5.0 Parts by weight of sodium salt of a disproportionated abietic acid

0.5 Parts by weight of sodium salt of a condensation product ofnaphthalene sulphonic acid and formaldehyde

0.5 Parts by weight of sodium hydroxide

0.5 Parts by weight of tetrasodium pyrophosphate

Polymerisation is carried out as in Example 1 and 2. The Mooneyviscosity ML-4'/100° C. of the resulting polymer is 45.

EXAMPLE 9 (Comparison Example)

Example 4 is similar to Example 3 except that instead of 0.28 parts byweight of n-dodecylmercaptan, 0.4 parts by weight of diethylxanthogendisulphide are used. The Mooney-viscosity ML-4'/100° C. of the resultingpolymer is 45.

II. Preparation of cross-linked, benzene insoluble polychloropreneEXAMPLE 10

The following components are introduced into a 40 liter autoclave whichis equipped with stirrer, thermometer, feed tubes and a cooling system:

14.4 kg of salt free water

0.815 kg sodium salt of a disproportionated abietic acid

0.072 kg sodium salt of a condensation product of alkyl naphthalenesulphonic acid and formaldehyde

0.036 kg sodium hydroxide

0.060 kg tetrasodium pyrophosphate

When these components have been thoroughly mixed, the following areadded:

10.620 kg of chloroprene

1.380 kg ethylene glycol dimethacrylate

0.034 kg n-dodecylmercaptan

The autoclave contents are then heated to 43° C. and polymerisation isinitiated with dropwise addition of a catalyst solution containing 2.5 gof formamidine sulphinic acid dissolved in 97.5 g of salt-free water.

When approximately 80% of the monomers have been converted to polymer,polymerisation is stopped by the addition of a stabilizer solution of

5 g of phenothiazine,

5 g of p-tert.-butyl pyrocatechol,

500 g of toluene.

The latex is then freed from unreacted monomers by steam distillation.The Mooney viscosity ML-4'/100° C. of the polymer is 70.

III Preparation of mixtures of uncross-linked and cross-linkedpolychloroprene EXAMPLE 11-18

In each of Examples 6- 9, 55 parts by weight (based on the solidscontent) of the polymer latices of Examples 1 to 4 are mixed with 45parts by weight (based on the solids content) of the polymer latex fromExample 5, precipitated by freeze coagulation and dried.

In each of Examples 10- 13, 85 parts by weight, (based on the solidscontent) of the polymer latices of Examples 1- 4 are mixed with 15 partsby weight (based on the solids content) of the polymer latex fromExample 5, precipitated by freeze coagulation and dried.

The polymer mixtures of Examples 6 to 13 are then mixed with thefollowing components on rollers in the usual manner:

100.0 Parts by weight polymer mixture

29.0 Parts by weight inactive carbon black

0.5 Parts by weight stearic acid

2.0 Parts by weight phenyl-β-naphthylamine

4.0 Parts by weight magnesium oxide

5.0 Parts by weight zinc oxide

0.5 Parts by weight ethylene thiourea.

The mixtures are vulcanized at 150° C. for 30 minutes. The vulcanizateobtained in this way have the properties shown in Table I.

The results demonstrate convincingly that the highest strengths areobtained when the mixtures contain polymers which have been preparedusing the particular xanthogen disulphides.

                                      Table I                                     __________________________________________________________________________                             Examples                                                                      11 12 13 14 15 16 17 18                              __________________________________________________________________________    Tensile strength (kp/cm.sup.2) DIN 53504                                                               121                                                                              122                                                                              109                                                                              115                                                                              140                                                                              153                                                                              130                                                                              133                             Elongation at break (%) DIN 53504                                                                      445                                                                              455                                                                              445                                                                              450                                                                              560                                                                              585                                                                              585                                                                              550                             Modulus (300% elongation in kp/cm.sup.2) DIN 53504                                                     63 60 55 57 54 59 41 48                              Shore hardness A at RT DIN 53505                                                                       58 57 56 56 57 56 53 54                              Elasticity DIN 53512     54 54 50 51 56 55 52 53                              __________________________________________________________________________

We claim:
 1. An xanthogen disulphide of the formula ##STR22## wherein Xmay be the same or different and is selected from the group consistingof hydrogen, alkyl having 1 to 6 carbon atoms, phenyl, naphthyl, benzyl,chlorine, bromine and iodine and each n is an integer of from 1 to 20.2. The xanthogen disulphide of claim 1 wherein the X groups are hydrogenor alkyl having 1 to 6 carbon atoms.